CN107556467B - It is a kind of for being catalyzed the catalyst of carbon dioxide Yu cyclohexene oxide copolymerization polycyclohexene - Google Patents
It is a kind of for being catalyzed the catalyst of carbon dioxide Yu cyclohexene oxide copolymerization polycyclohexene Download PDFInfo
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Abstract
The invention discloses a kind of for being catalyzed the catalyst of carbon dioxide Yu cyclohexene oxide copolymerization polycyclohexene, the catalyst for being catalyzed carbon dioxide and cyclohexene oxide copolymerization polycyclohexene is 3- ethoxy-benzaldehyde contracting 1, 2- propane diamine Zn complex, the invention also discloses the methods using the catalyst carbon dioxide for being catalyzed carbon dioxide and cyclohexene oxide copolymerization polycyclohexene and cyclohexene oxide copolymerization polycyclohexene, reaction pressure is 3 ~ 6MPa, reaction temperature is 80 ~ 160 DEG C, reaction time is 12 ~ 50h, the present invention is under above-mentioned reaction condition, the fatty poly-ester carbonate of available different molecular weight, catalytic efficiency is up to 195.8g polymer/g catalyst, poly- carbon in copolymer Acid esters molar content is more than 92%.The catalyst preparation is simple, and catalytic efficiency and selectivity are good.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to one kind is total for being catalyzed carbon dioxide and cyclohexene oxide
Aggregate into the catalyst of polycyclohexene.
Background technique
Currently, the gases such as carbon dioxide, methane, nitrogen oxides, freon are considered as the main original for leading to global warming
Cause.Statistical research shows that carbon dioxide accounts for 2/3rds of all greenhouse gases summations to the contribution of global warming, thus
Cause the greenhouse effects got worse.It is more than 24,000,000,000 tons that the whole world is discharged into the carbon dioxide in atmosphere every year, wherein about
15000000000 tons of photosynthesis by plant absorbs, therefore has a net increase of about 9,000,000,000 tons of carbon dioxide in annual atmosphere.To reduce its influence, remove
The discharge of carbon dioxide is limited outer, another effective measures is exactly to be recycled benefit to these carbon dioxide generated
With being translated into chemicals, fuel or other useful products.There are 1.1 hundred million tons of carbon dioxide to be used in chemicals every year at present
In, it is mainly used in the industrial production of urea, salicylic acid, methanol, cyclic carbonate and polycarbonate, wherein urea occupancy
80%.Except above-mentioned industrial production, other there are also be much among research.
Wherein carrying out copolyreaction using carbon dioxide and epoxide is considered as very promising titanium dioxide
Carbon utilizes method, and the fatty poly-ester carbonate of preparation has biological degradability, has good biocompatibility and physical mechanical
Performance, and there are many type, can further be improved its performance, be met by changing backbone chemistry structure and introducing functional group
The needs of various aspects.Carbon dioxide and ethylene oxide are copolymerized the poly (propylene carbonate) prepared and itself and cyclohexene oxide is copolymerized and prepares
Polycyclohexene most study, and polycyclohexene glass transition temperature is high, and mechanical property is good, has more preferable
Application prospect.But carbon dioxide chemical stability with higher, inertia, therefore the copolymerization are shown for copolyreaction
Reaction needs to select suitable catalyst, and catalytic activity with higher can sufficiently activate carbon dioxide, and need very
Good reaction selectivity improves the content of carbonic ester chain link in copolymerization product, obtains purer fatty poly-ester carbonate.At present
The carbon dioxide and epoxide copolyreaction catalyst of the exploitation mostly catalyst containing zinc, including more proton alcohol zinc systems,
Dicarboxylic Acids zinc system, rare earth compound system, high steric-hindrance amino beta-diimine Zn complex system etc..Although carbon dioxide with
The copolyreaction research of epoxide makes some progress, but develops new and effective, stable catalyst and be in
Primary stage.
Summary of the invention
Aiming at the problems existing in the prior art, the present invention provides a kind of total for being catalyzed carbon dioxide and cyclohexene oxide
The catalyst of polycyclohexene is aggregated into, which has the advantages that high catalytic efficiency, selectivity are good, has very high
Practical application value.
In order to solve the above technical problems, the invention adopts the following technical scheme:
It is a kind of for being catalyzed the catalyst of carbon dioxide Yu cyclohexene oxide copolymerization polycyclohexene, the use
It is 3- ethoxy-benzaldehyde contracting 1 in being catalyzed catalyst of the carbon dioxide with cyclohexene oxide copolymerization polycyclohexene,
3- propane diamine Zn complex, structural formula are as follows:
。
The 3- ethoxy-benzaldehyde contracting 1,3- propane diamine Zn complex the preparation method is as follows:
(1) 3- ethoxy-benzaldehyde and 1 are taken, 3- propane diamine is dissolved in methanol respectively, at room temperature 3- while stirring
Ethoxy-benzaldehyde solution is added drop-wise in 1,3- propane diamine solution, after being added dropwise, is heated to reflux, and 1 ~ 2h of stirring is continued, filtering
Sediment out, it is dry, obtain 3- ethoxy-benzaldehyde contracting 1,3- propane diamine ligand；
(2) by 3- ethoxy-benzaldehyde and 1,3- propane diamine ligand is put into container, to container vacuum-pumping, is then charged with nitrogen
Gas is added toluene and dissolves 3- ethoxy-benzaldehyde and 1,3- propane diamine ligand is cooling in ice salt bath under nitrogen protection to normal pressure
The lower toluene solution that diethyl zinc is added removes ice salt bath after stirring 1h, stirring at normal temperature 1h, and toluene and not anti-is taken in decompression away
The diethyl zinc answered obtains 3- ethoxy-benzaldehyde and 1,3- propane diamine Zn complex.
The molar ratio of 3- ethoxy-benzaldehyde and 1,3- propane diamine is 2 ~ 2.2:1 in the step (1).
In the step (2) molar ratio of 3- ethoxy-benzaldehyde contracting 1,3- propane diamine ligand and diethyl zinc be 1:1 ~
1.2。
Using described for being catalyzed the catalyst of carbon dioxide Yu cyclohexene oxide copolymerization polycyclohexene
The method for being catalyzed carbon dioxide and cyclohexene oxide copolymerization polycyclohexene, steps are as follows: by 3- ethoxy benzonitrile
Aldehyde contracts in 1,3- propane diamine Zn complex catalyst merging autoclave, and displacement carbon dioxide is vacuumized at 80 DEG C for several times, is cooled to
Room temperature squeezes into cyclohexene oxide in autoclave, is pressurized to 3 ~ 6MPa, is warming up to 80 ~ 160 DEG C, heats 12 ~ 50h, then cools down
To room temperature, polymer is dissolved out from autoclave with methylene chloride, using methanol as precipitating reagent, is dripped dichloromethane solution under stirring
Enter in methanol, after the solid that settles out is collected by filtration, 50 DEG C of vacuum drying obtain polycyclohexene.
The mass ratio of the 3- ethoxy-benzaldehyde contracting 1,3- propane diamine Zn complex and cyclohexene oxide be 1:200 ~
500。
The present invention is under above-mentioned reaction condition, the fatty poly-ester carbonate of available different molecular weight, catalytic efficiency
Up to 195.8g polymer/g catalyst, polycarbonate molar content is more than 92% in copolymer.Catalyst preparation letter
Single, catalytic efficiency and selectivity are good.
Specific embodiment
Combined with specific embodiments below, the present invention will be further described.It should be understood that following embodiment is merely to illustrate this
The person skilled in the art of the range of invention and is not intended to limit the present invention, the field can make one according to the content of foregoing invention
A little nonessential modifications and adaptations.
Embodiment 1
The catalyst for being used to be catalyzed carbon dioxide Yu cyclohexene oxide copolymerization polycyclohexene of the present embodiment
3- ethoxy-benzaldehyde contracting 1,3- propane diamine Zn complex the preparation method is as follows:
(1) 1.65g(0.011mol) 3- ethoxy-benzaldehyde is dissolved in 20mL methanol respectively, 0.37g (0.005mol)
1,3- propane diamine is dissolved in 20mL methanol, and at room temperature, 3- ethoxy-benzaldehyde solution is added drop-wise in 1,3- propane diamine solution, drop
It is heated to reflux after adding, continues to stir 1h, filter out sediment, it is dry, it obtains 3- ethoxy-benzaldehyde contracting 1,3- propane diamine and matches
Body；The structural formula of 3- ethoxy-benzaldehyde contracting 1,3- propane diamine ligand are as follows:
Its structural characterization is
1H NMR (400 MHz, CDCl3): δ 1.42(t, 6H ,-CH3), 2.2 (m, 2H ,-CH2), 3.82
(t, 4H ,-CH2), 4.3 (m, 4H ,-CH2), 6.3-7.5(m, 8H, aromatic H)；
(2) it weighs 3.38g (0.01mol) 3- ethoxy-benzaldehyde contracting 1,3- propane diamine ligand to be put into container, vacuumize,
20mL toluene dissolution 3- ethoxy-benzaldehyde contracting 1,2- propane diamine ligand is added under nitrogen protection in inflated with nitrogen, cold in ice salt bath
Lower that the toluene solution (10 vol %) for containing 1.482g (0.012mol) diethyl zinc is added, after stirring 1h, ice salt bath is removed,
Stirring at normal temperature 1h, decompression take solvent and unreacted diethyl zinc away to get 3- ethoxy-benzaldehyde contracting 1,2- propane diamine zinc
Composition catalyst.
Embodiment 2
The catalyst for being used to be catalyzed carbon dioxide Yu cyclohexene oxide copolymerization polycyclohexene of the present embodiment
3- ethoxy-benzaldehyde contracting 1,3- propane diamine Zn complex the preparation method is as follows:
(1) 1.5g (0.01mol) 3- ethoxy-benzaldehyde is dissolved in 20mL methanol respectively, 0.37g (0.005mol) 1,
3- propane diamine is dissolved in 20mL methanol, and at room temperature, 3- ethoxy-benzaldehyde solution is added drop-wise in 1,3- propane diamine solution, is added dropwise
It is heated to reflux after complete, continues to stir 2h, filter out sediment, it is dry, obtain 3- ethoxy-benzaldehyde contracting 1,3- propane diamine ligand；
(2) it weighs 3.38g (0.01mol) 3- ethoxy-benzaldehyde contracting 1,3- propane diamine ligand to be put into container, vacuumize,
20mL toluene dissolution 3- ethoxy-benzaldehyde contracting 1,3- propane diamine ligand is added under nitrogen protection in inflated with nitrogen, cold in ice salt bath
Lower that the toluene solution (10 vol %) for containing 1.235g (0.01mol) diethyl zinc is added, after stirring 1h, ice salt bath is removed,
Stirring at normal temperature 1h, decompression take solvent and unreacted diethyl zinc away to get 3- ethoxy-benzaldehyde contracting 1,3- propane diamine zinc
Composition catalyst.
Embodiment 3
Utilize 3- ethoxy-benzaldehyde contracting 1,3- propane diamine Zn complex catalysis carbon dioxide and cyclohexene oxide combined polymerization
It is as follows at the method for polycyclohexene:
Claim to take out at 80 DEG C in 0.1g 3- ethoxy-benzaldehyde contracting 1,3- propane diamine Zn complex catalyst merging autoclave
Vacuum displacement carbon dioxide for several times, is cooled to room temperature.20g cyclohexene oxide is squeezed into autoclave, 3MPa is pressurized to, is warming up to
80 DEG C, 20h is heated, is then cooled to room temperature；Polymer is dissolved out from autoclave with methylene chloride, using methanol as precipitating reagent,
Dichloromethane solution is instilled in methanol under stirring, after the solid that settles out is collected by filtration, is dried in vacuo, is obtained with 50 DEG C of vacuum oven
To polycyclohexene 10.32g, polycarbonate molar content is 92% in copolymer.
Embodiment 4
Utilize 3- ethoxy-benzaldehyde contracting 1,3- propane diamine Zn complex catalysis carbon dioxide and cyclohexene oxide combined polymerization
It is as follows at the method for polycyclohexene:
Claim to take out at 80 DEG C in 0.1g 3- ethoxy-benzaldehyde contracting 1,3- propane diamine Zn complex catalyst merging autoclave
Vacuum displacement carbon dioxide for several times, is cooled to room temperature, and 50g cyclohexene oxide is squeezed into autoclave, 4MPa is pressurized to, is warming up to
120 DEG C, 25h is heated, is then cooled to room temperature；Polymer is dissolved out from autoclave with methylene chloride, using methanol as precipitating reagent,
Dichloromethane solution is instilled in methanol under stirring, after the solid that settles out is collected by filtration, is dried in vacuo, is obtained with 50 DEG C of vacuum oven
To polycyclohexene 19.58g, polycarbonate molar content is 95% in copolymer.
Embodiment 5
Utilize 3- ethoxy-benzaldehyde contracting 1,3- propane diamine Zn complex catalysis carbon dioxide and cyclohexene oxide combined polymerization
It is as follows at the method for polycyclohexene:
Claim to take out at 80 DEG C in 0.1g 3- ethoxy-benzaldehyde contracting 1,3- propane diamine Zn complex catalyst merging autoclave
Vacuum displacement carbon dioxide for several times, is cooled to room temperature, and 30g cyclohexene oxide is squeezed into autoclave, 6MPa is pressurized to, is warming up to
160 DEG C, 50h is heated, is then cooled to room temperature；Polymer is dissolved out from autoclave with methylene chloride, using methanol as precipitating reagent,
Dichloromethane solution is instilled in methanol under stirring, after the solid that settles out is collected by filtration, is dried in vacuo, is obtained with 50 DEG C of vacuum oven
To polycyclohexene 14.83g, polycarbonate molar content is 96% in copolymer.
Embodiment 6
Utilize 3- ethoxy-benzaldehyde contracting 1,3- propane diamine Zn complex catalysis carbon dioxide and cyclohexene oxide combined polymerization
It is as follows at the method for polycyclohexene:
Claim to take out at 80 DEG C in 0.1g 3- ethoxy-benzaldehyde contracting 1,3- propane diamine Zn complex catalyst merging autoclave
Vacuum displacement carbon dioxide for several times, is cooled to room temperature, and 20g cyclohexene oxide is squeezed into autoclave, 4MPa is pressurized to, is warming up to
100 DEG C, 12h is heated, is then cooled to room temperature；Polymer is dissolved out from autoclave with methylene chloride, using methanol as precipitating reagent,
Dichloromethane solution is instilled in methanol under stirring, after the solid that settles out is collected by filtration, is dried in vacuo, is gathered with vacuum oven
Cyclohexene carbonate 12.03g, polycarbonate molar content is 94% in copolymer.
Basic principles and main features and advantages of the present invention of the invention have been shown and described above.The skill of the industry
Art personnel it should be appreciated that the present invention is not limited to the above embodiments, the above embodiments and description only describe
The principle of the present invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these
Changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and
Its equivalent thereof.
Claims (6)
1. a kind of for being catalyzed the catalyst of carbon dioxide Yu cyclohexene oxide copolymerization polycyclohexene, feature exists
In: the catalyst for being catalyzed carbon dioxide and cyclohexene oxide copolymerization polycyclohexene is 3- ethoxybenzene
Formaldehyde contracting 1,3- propane diamine Zn complex, structural formula are as follows:
。
2. according to claim 1 for being catalyzed carbon dioxide and cyclohexene oxide copolymerization polycyclohexene
Catalyst, it is characterised in that: 3- ethoxy-benzaldehyde contracting 1,3- propane diamine Zn complex the preparation method is as follows:
(1) 3- ethoxy-benzaldehyde and 1 are taken, 3- propane diamine is dissolved in methanol respectively, at room temperature 3- ethoxy while stirring
Benzaldehyde solution is added drop-wise in 1,3- propane diamine solution, after being added dropwise, is heated to reflux, and 1 ~ 2h of stirring is continued, and it is heavy to filter out
Starch, it is dry, obtain 3- ethoxy-benzaldehyde contracting 1,3- propane diamine ligand；
(2) by 3- ethoxy-benzaldehyde and 1,3- propane diamine ligand is put into container, to container vacuum-pumping, is then charged with nitrogen extremely
Normal pressure is added toluene and dissolves 3- ethoxy-benzaldehyde and 1,3- propane diamine ligand adds in the case where ice salt bath is cooling under nitrogen protection
Enter the toluene solution of diethyl zinc, after stirring 1h, remove ice salt bath, stirring at normal temperature 1h, toluene and unreacted is taken in decompression away
Diethyl zinc obtains 3- ethoxy-benzaldehyde and 1,3- propane diamine Zn complex.
3. according to claim 2 for being catalyzed carbon dioxide and cyclohexene oxide copolymerization polycyclohexene
Catalyst, it is characterised in that: 3- ethoxy-benzaldehyde and 1 in the step (1), the molar ratio of 3- propane diamine are 2 ~ 2.2:1.
4. according to claim 2 for being catalyzed carbon dioxide and cyclohexene oxide copolymerization polycyclohexene
Catalyst, it is characterised in that: mole of the contracting of 3- ethoxy-benzaldehyde 1,3- propane diamine ligand and diethyl zinc in the step (2)
Than for 1:1 ~ 1.2.
5. using described in claim 1 for being catalyzed carbon dioxide and cyclohexene oxide copolymerization polycyclohexene
The method of catalyst carbon dioxide and cyclohexene oxide copolymerization polycyclohexene, it is characterised in that step is such as
Under: by 3- ethoxy-benzaldehyde contracting 1,3- propane diamine Zn complex catalyst merging autoclave, displacement two is vacuumized at 80 DEG C
Carbonoxide for several times, is cooled to room temperature, and cyclohexene oxide is squeezed into autoclave, is pressurized to 3 ~ 6MPa, is warming up to 80 ~ 160 DEG C, adds
12 ~ 50h of heat, then cools to room temperature, and polymer is dissolved out from autoclave with methylene chloride, using methanol as precipitating reagent, stirring
Lower to instill dichloromethane solution in methanol, after the solid that settles out is collected by filtration, 50 DEG C of vacuum drying obtain poly- carbonic acid cyclohexene
Ester.
6. according to claim 5 for being catalyzed carbon dioxide and cyclohexene oxide copolymerization polycyclohexene
The method of catalyst carbon dioxide and cyclohexene oxide copolymerization polycyclohexene, it is characterised in that: the 3-
The mass ratio of ethoxy-benzaldehyde contracting 1,3- propane diamine Zn complex and cyclohexene oxide is 1:200 ~ 500.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101974024A (en) * | 2010-09-06 | 2011-02-16 | 河北工业大学 | Salen-metal complex, preparation method and application thereof |
| CN101972674A (en) * | 2010-09-06 | 2011-02-16 | 河北工业大学 | Catalyst used for coupling reaction of carbon dioxide and epoxy compound |
| CN103755943A (en) * | 2013-07-25 | 2014-04-30 | 河南理工大学 | Catalyst and method of preparing polycarbonate cyclohexene ester by using catalyst |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101974024A (en) * | 2010-09-06 | 2011-02-16 | 河北工业大学 | Salen-metal complex, preparation method and application thereof |
| CN101972674A (en) * | 2010-09-06 | 2011-02-16 | 河北工业大学 | Catalyst used for coupling reaction of carbon dioxide and epoxy compound |
| CN103755943A (en) * | 2013-07-25 | 2014-04-30 | 河南理工大学 | Catalyst and method of preparing polycarbonate cyclohexene ester by using catalyst |
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Effective date of registration: 20211203 Address after: 257300 north of Gangcheng road and east of Gangxi Third Road, dongyinggang Economic Development Zone, Dongying City, Shandong Province Patentee after: SHANDONG DESHI CHEMICAL Co.,Ltd. Address before: 451191 Xianghe Road, Longhu Town, Zhengzhou City, Henan Province Patentee before: HENAN INSTITUTE OF ENGINEERING |